高效光催化二氧化碳还原钻单原子催化剂的多尺度结构工程  

Multiscale structural engineering of cobalt single-atom catalyst for highly efficient photocatalytic CO_(2) reduction

作　　者：王榆惠 郑天宇 金昱丞 孙婷婷 丁旭 王萧 徐清梅 李彤轩 张少龙 姜建壮 Yuhui Wang;Tianyu Zheng;Yucheng Jin;Tingting Sun;Xu Ding;Xiao Wang;Qingmei Xu;Tongxuan Li;Shaolong Zhang;Jianzhuang Jiang(Bejing Advanced Innovation Center for Materials Genome Engineering,Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials,Department of Chemistry and Chemical Engineering,School of Chemistry and Biological Engineering,University of Science and Technology Beijing,Beijing 100083,China;College of Chemistry and Environmental Engineering,Shenzhen University,Shenzhen 518060,China)

机构地区：[1]Beijing Advanced Innovation Center for Materials Genome Engineering,Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials,Department of Chemistry and Chemical Engineering,School of Chemistry and Biological Engineering,University of Science and Technology Beijing,Beijing 100083,China [2]College of Chemistry and Environmental Engineering,Shenzhen University,Shenzhen 518060,China

出　　处：《Science China Materials》2024年第4期1292-1300,共9页中国科学（材料科学）（英文版）

基　　金：financially supported by the National Natural Science Foundation of China (11293064 and 22001015);the Fundamental Research Funds for the Central Universities (2050205)。

摘　　要：人工光合作用将二氧化碳转化为增值化学品和燃料,在克服全球环境能源危机方面具有巨大潜力.然而,由于CO_(2)的热力学稳定性和动力学滞后性,开发高效的CO_(2)RR光催化剂是一个巨大的挑战.本文在微介孔氮掺杂碳(0.8-Co-ISAS/MMNC-900)上制备了一种具有高度分散Co单原子位的分级多孔钴单原子光催化剂,该催化剂显著促进了CO_(2)-to-CO的光还原.0.8-Co-ISAS/MMNC-900催化剂的CO生成速率高达7261μmol g^(-1)h^(-1),CO选择性高达90.1%,并且在四次循环测试中表现出良好的稳定性.实验数据和理论结果表明,分层多孔结构可以促进电荷分离引起的外部局部电场的形成,Co隔离的单原子位和微介孔构型协同作用,促进光激发电子积累、CO_(2)吸附活化和*COOH中间体的形成.本研究通过多尺度多孔结构工程,提出了一种合成CO_(2)还原光催化剂的新策略.Artificial photosynthesis,which converts CO_(2) into value-added chemicals and fuels,is of enormous potential in overcoming both global environmental problems and energy crisis.However,the development of CO_(2) photoconversion catalysts with high efficiency remains a great challenge due to the thermodynamic stability and dynamics sluggishness of CO_(2).Herein,a superior hierarchical porous cobalt singleatom photocatalyst featuring highly dispersed Co isolated single atomic sites on micro-mesoporous nitrogen-doped carbon(0.8-Co-ISAS/MMNC-900)is developed and characterized,which significantly boosts the photoreduction of CO_(2)-to-CO.The 0.8-Co-ISAS/MMNC-900 catalyst achieves a high 7261μmol g^(-1)h^(-1) CO formation rate,an impressive 90.1%CO selectivity,as well as an decent stability during four times cycling test,indicating a boosted CO_(2) photoconversion property.Experimental data and theoretical results reveal that the hierarchically porous structure can promote the formation of exterior local electric field caused by charge separation as well as the synergic role of Co ISASs and micro-mesoporous configuration can facilitate photo-excited electron accumulation,CO_(2) adsorption and activation,and*COOH intermediate formation.This work develops a novel strategy to synthesize superior photocatalysts for CO_(2) reduction through multiscale porous structural engineering.

关 键 词：单原子 热力学稳定性 激发电子 光还原 多尺度结构 人工光合作用 多孔结构 电荷分离 

分 类 号：O643.36[理学—物理化学] O644.1[理学—化学]